Electrically conductive polymers with enhanced conductivity

ABSTRACT

An electrically conductive polymer linked to conductive nanoparticle is provided. The conductive polymer can include conductive monomers and one or more monomers in the conductive polymer can be linked to a conductive nanoparticle and can include a polymerizable moiety so that it can be incorporated into a polymer chain. The electrically conductive monomer can include a 3,4-ethylenedioxythiophene as a conductive monomer. The electrically conductive polymer having the conductive nanoparticle can be prepared into an electrically conductive layer or film for use in electronic devices.

TECHNICAL FIELD

The present disclosure relates generally to polymerizable compositionsand techniques for producing electrically conductive polymers withenhanced conductivity.

BACKGROUND

Electrical conductivity is an important parameter for the operation ofmany devices. As devices become smaller, there has been a need atimproving electrical conductivity without increasing the size of theconductive entity or even a need for a reduction in size. The size ofconducting members can play a role in the development and improvement oftransparent electrodes, electromagnetic wave shielding films, antistaticagents, solar cells and the like.

Currently, electrical conductivity is achieved in transparent films byapplication of a thin metallic coating such as gold, silver or copper,or a metal oxide coating such as Indium Tin Oxide (ITO). Transparentconductive oxide films such as ITO are used in a wide variety ofapplications such as for window de-icers, heat reflectors, LCDs, organiclight emitting diodes (OLEDs), solar cells, and architectural coatings.However, ITO coatings have many limitations such as weak mechanicalstrength and low flexibility, which can result in being fragile andreadily damaged during bending. Also, the ITO coatings are generallyapplied using vacuum deposition, and are not able to form patterns orcircuits. Also, the high raw material cost of indium and the chemicalstability in some device structures limit potential applications. Forbetter conductivity control and mechanical property demands (i.e.,flexibility, expansion coefficient, etc), alternative highly conductivematerials with more favorable mechanical properties are needed.Moreover, in consideration of the display industry pursuing lightweight-, low cost- and large size-products, there is a need to developconductive materials to improve upon and advance past ITO.

Some conductive materials that may replace ITO can include carbonnanotubes, conductive polymers, or their composite materials. Singlewall carbon nanotubes (SWCNTs) are candidates for a transparentconductive film, since they are robust, giving them the potential to bedeposited on plastic and flexed with no degradation in electricalconductivity. Carbon nanotube coatings may require less loading (perweight percent) than other conductive particles.

SUMMARY

Electrically conductive polymers can be prepared from monomers that arelinked to an electrically conductive nanoparticle according toembodiments described herein. Such electrically conductive polymers cancontain conductive monomers and monomers linked to conductivenanoparticles, and can be prepared into electrically conductive layersor films for use in electronic devices.

In one embodiment, a monomer can comprise a conductive nanoparticle anda polymerizable moiety linked to the nanoparticle. The polymerizablemoiety can include an electrically conductive monomer, such as a3,4-ethylenedioxythiophene or any other conductive monomer. Optionally,the polymerizable moiety can include a cationic monomer, anionicmonomer.

In one embodiment, the polymerizable moiety can be linked to thenanoparticle through a linker. The linker can include any type oflinking group, such as hydrocarbon, or any suitable linker. Somehydrocarbon examples can include alkylthio, alkenylthio, alkynylthio, oralkoxythio, which is unsubstituted or substituted.

In one embodiment, the conductive polymer can include one or moreconductive monomers and a conductive nanoparticle linked to the polymer.The conductive nanoparticle can be linked to the polymer through aconductive monomer.

In one embodiment, the conductive polymer can include one or moremonomers having a structure of Formula 2:

B is selected from the group of phenylene, phenylene vinylene,pyrrolylene, pyrrolylene vinylene, thienylene, thienylene vinylene,fluorenylene, fluorenylene vinylene, furanylene, furanylene vinylene,phenothiazinylene, phenothiazinylene vinylene, phenazinylene,phenazinylene vinylene, phenoxazinylene and phenoxazinylene vinylene,which is unsubstituted or substituted with one or more substituents. Thesubstituents are independently selected from the group of hydroxyl,alkyl, alkenyl, alkynyl, alkanoyl, alkanoylamino, alkenoyl, alkynoyl,alkoxy, alkoxycarbonyl, alkoxycarbonylamino, alkylamino,alkylaminocarbonyl, dialkylaminocarbonyl, alkylsulfonyl, alkylsulfinyl,sulfonylaminoalkyl, alkylsulfonylaminocarbonyl, aminoalkyl, cyanoalkyl,halogen, haloalkyl, haloalkenyl, haloalkynyl, haloalkanoyl,haloalkenoyl, haloalkynoyl, haloalkoxy, haloalkoxycarbonyl,hydroxyalkyl, oxoalkyl, cycloalkyl, cycloalkenyl, cycloalkanoyl,cycloalkenoyl, cycloalkoxy, cycloalkoxycarbonyl, aryl, arylene,heterocycle, heterocyclyl, heteroaryl, heteroarylene, arylalkyl,heteroarylalkyl, arylalkanoyl, heteroarylalkanoyl, arylalkenoyl,heteroarylalkenoyl, arylalkynoyl, heteroarylalkynoyl, arylalkoxy,heteroarylalkoxy, aryloxy, heteroaryloxy, aryloxycarbonyl,heteroarylxoycarbonyl, arylalkoxycarbonyl, heteroarylalkoxycarbonyl,alkylthio, alkylthioalkyl, arylthio, arylsulfonyl and arylsulfinyl, orthe substituents together may form an alkylene or alkenylene chaincompleting a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring having0 or more divalent nitrogen, sulfur or oxygen atoms. These substituentscan be further substituted or unsubstituted. R₁ is L-G, wherein G is ametal nanoparticle and L is a linker.

In one embodiment, the conductive polymer can include one or moremonomers having a structure of Formula 1, where A can independently beany of the groups described in connection with B of Formula 2.

In one embodiment, the monomer can have a structure of Formula 3,Formula 4, or Formula 5, or analog or derivative thereof:

In Formulas 3-5, X₁, X₂ and X₃ are independently NH, O, S or PH; and R₂,R₂′, R₃, R₃′, R₄ and R₄′ are substituents, and one or more of thesubstituents is linked to the nanoparticle.

In one embodiment, the subtituents are independently selected from thegroups: hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, alkanoyl,alkanoylamino, alkenoyl, alkynoyl, alkoxy, alkoxycarbonyl,alkoxycarbonylamino, alkylamino, alkylaminocarbonyl,dialkylaminocarbonyl, alkylsulfonyl, alkylsulfinyl, sulfonylaminoalkyl,alkylsulfonylaminocarbonyl, aminoalkyl, cyanoalkyl, halogen, haloalkyl,haloalkenyl, haloalkynyl, haloalkanoyl, haloalkenoyl, haloalkynoyl,haloalkoxy, haloalkoxycarbonyl, hydroxyalkyl, oxoalkyl, cycloalkyl,cycloalkenyl, cycloalkanoyl, cycloalkenoyl, cycloalkoxy,cycloalkoxycarbonyl, aryl, arylene, heterocycle, heterocyclyl,heteroaryl, heteroarylene, arylalkyl, heteroarylalkyl, arylalkanoyl,heteroarylalkanoyl, arylalkenoyl, heteroarylalkenoyl, arylalkynoyl,heteroarylalkynoyl, arylalkoxy, heteroarylalkoxy, aryloxy,heteroaryloxy, aryloxycarbonyl, heteroarylxoycarbonyl,arylalkoxycarbonyl, heteroarylalkoxycarbonyl, alkylthio, alkylthioalkyl,arylthio, arylsulfonyl and arylsulfinyl; or R₂ and R₂′ or R₃ and R₃′ orR₄ and R₄′ together form a 3, 4, 5, 6, or 7-membered aromatic oralicyclic ring having carbons or heteroatoms of N, S, or O; which issubstituted or unsubstituted.

In one embodiment, the conductive nanoparticle can be naked or includeone or more solvent compatible groups. For example, the solventcompatible groups can be hydrophilic moieties.

In one embodiment, the nanoparticle can be linked to hydrophilicmoieties that have Formula 6; one of R₅, R₆ and R₇ has Formula 7 and theothers are independently hydrogen, hydroxyl, alkyl, or alkoxy; Q is analkylene having from one or two carbons; d is 1 to 3; and R₈ iscarboxylic acid, sulfonic acid, or a straight or branched alkyl, whichis substituted with thiol.

In one embodiment, a composition can include a conductive polymer linkedto a conductive nanoparticle. The conductive monomer can include a3,4-ethylenedioxythiophene. The conductive monomer can include astructure of Formula 3, Formula 4, or Formula 5, or analog or derivativethereof as described herein.

In one embodiment, the conductive polymer can optionally be doped withone or more polymeric acids. For example, such polymeric acid can bestyrenesulfonate.

In one embodiment, a composition can have a sufficient ratio of theconductive monomer and the monomer linked to the nanoparticle to conductelectricity.

In one embodiment, the composition can include a monomer having aphotoreactive group. The photoreactive group can be at any of the Rgroups. For example, the photoreactive group can be selected from thegroup consisting of a cinnamoyl group, a chalcone group, a coumaringroup, a maleimide group, an anthracenic group and a pyrimidine group,which is unsubstituted or substituted. A substituted group can includean ionic moiety. Also, the monomer can be in a polymerizable compositionor within a polymer, which can include the monomer being a monomer of apolymer or being positioned within a polymer network.

In one embodiment, a polymer can include a conductive monomer and amonomer linked to a conductive nanoparticle. The polymer can beconfigured to have a sufficient ratio of the conductive monomer and themonomer linked to the nanoparticle to conduct electricity.

In an illustrative embodiment, an electronic device can include anelectrically conductive polymer that has a conductive monomer and amonomer linked to a conductive nanoparticle. The conductive polymer canbe an electrically conductive layer, film, or coating. Examples ofelectronic devices include light-emitting diodes, light emitting diodedisplays, liquid crystral displays, electronic paper, touchscreens,diode lasers, photodetectors, photoconductive cells, photoresistors,photoswitches, phototransistors, phototubes, IR detectors, photovoltaicdevices, solar cells, transistors, diodes, memory storage devices,antistatic films biosensors, electrochromic devices, solid electrolytecapacitors, energy storage devices, electromagnetic wave shieldingfilms, window de-icers, heat reflectors, architectural materialselectro-optic modulators, microresonators, interferometers, opticalswitches, directional couplers and multiplexers.

In one embodiment, a kit can include a conductive monomer and a monomerlinked to a conductive nanoparticle.

The foregoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, embodiments,and features described above, further aspects, embodiments, and featureswill become apparent by reference to the drawings and the followingdetailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1C illustrate methods of preparing illustrative examples ofconductive polymers.

DETAILED DESCRIPTION

In the following detailed description, reference is made to theaccompanying drawings, which form a part hereof. In the drawings,similar symbols typically identify similar components, unless contextdictates otherwise. The illustrative embodiments described in thedetailed description, drawings, and claims are not meant to be limiting.Other embodiments may be utilized, and other changes may be made,without departing from the spirit or scope of the subject matterpresented herein. It will be readily understood that the aspects of thepresent disclosure, as generally described herein, and illustrated inthe figures, can be arranged, substituted, combined, separated, anddesigned in a wide variety of different configurations, all of which areexplicitly contemplated herein.

Generally, a conductive polymer composition can be prepared to includeone or more electrically conducting polymers or copolymers with one ormore monomers being linked to a conductive nanoparticle. Theelectrically conducting polymer can be prepared from one or more typesof electrically conductive monomers that can pass electrical current.The polymer can include a sufficient amount of monomers being linkedtogether such that the conductive polymer composition is capable ofpassing electrical current in any amount or load. A single conductivepolymer chain or a polymer network composition thereof may be capable ofpassing an electrical current. Accordingly, the number of nanoparticlesper polymer strand or polymer network can be varied as desired or neededfor a particular application.

The conductive polymer can have one or more different types ofelectrically conductive monomers as well as a monomer linked to aconductive nanoparticle. The monomer linked to the conductivenanoparticle can include a polymerizable moiety. The conductive polymercan have the different monomers in various sequences or distributions,such as block, alternating, random, or other configuration, order orarrangement. The electrically conductive monomers can be selected basedon any structural or functional application to the polymer. Thedifferent types of conductive monomers can be selected to provide forsufficient or optimal electrical conductivity, and can be included inany number, ratio, electric potential or other parameter.

In one embodiment, the electrically conductive polymer can be doped withone or more polymeric acids. The polymeric acids are doped with theconductive polymer in the form of an ionic bond. Any polymeric acids canbe doped with the conductive polymer so long as the polymeric acids donot reduce the solubility of the conductive polymer. The polymeric acidscan be used for providing charges on the conductive polymer to elevateelectrical conductivity. Such polymeric acids includespoly(styrenesulfonate)

In one embodiment, a 3,4-ethylenedioxythiophene can be comprised in theelectrically conductive polymer as an electrically conductive monomer.The electrically conductive polymer can be apoly(3,4-ethylenedioxythiophene), or can include one or more segments ofpoly(3,4-ethylenedioxythiophene) (PEDOT) in any number, order,arrangement, or amount, as well as 3,4-ethylenedioxythiophene monomersin any number, order, arrangement, or amount. PEDOT carries positivecharges and is based on polythiophene. Thepoly(3,4-ethylenedioxythiophene) can include one or more3,4-ethylenedioxythiophene monomers that are substituted orunsubstituted with R groups as described herein, wherein thesubstitutions can be at any hydrogen, if possible. For example, thehydrogen atoms of the ethylene group can substituted with R groups. Thedifferent substituted monomers can be arranged in any amount or order toprovide desired or beneficial chemical or physical characteristics.

Additional examples of conductive polymers can includepolyphenylenevinylenes, polyacetylenes, polythiophenes, polypyrroles,polyphenylene sulfides, polyalkylthiophenes, polyindoles, polypyrenes,polycarbazoles, polyazulenes, polyazepines, polynaphthalenes, andothers. Accordingly, any of these conductive polymers can be linked to aconductive nanoparticle. Also, any of the monomers of these conductivepolymers can be included in the conductive polymer without being linkedto a conductive nanoparticle.

In one embodiment, the conductive nanoparticle can be a highlyconductive particle having a high conductive density, such as but notlimited to, a metal nanoparticle such as a gold nanoparticle.

In one embodiment, the conductive nanoparticle can be coupled withhydrophilic moieties. The hydrophilic moiety can be any water solublesubstance, such as but not limited to a polymer like polyethyleneglycol, that can be coupled with the nanoparticle to improve watercompatibility. The hydrophilic moieties can be used to aid in suspendingthe nanoparticle within the conductive polymer or a conducting channelformed thereofrom as well as in an aqueous solvent. The hydrophilicmoieties can be selected for tailoring the conductive polymer and canprovide a non-uniform arrangement within the ionic polymer complex.Also, the hydrophilic moieties can increase the ability of theconductive polymer and nanoparticle to be suspended to improve use inwet fabrication techniques or water-based applications.

In one embodiment, a monomer can be linked to the conductivenanoparticle through a linker. For example, a monomer having a thiolbased alkyl substituent can be coupled to the conductive nanoparticle,such as a metal nanoparticle. The methods of preparing thenanoparticle-linked monomer can use conventional preparation method ofgold nanoparticle conjugation. The types and amounts ofnanoparticle-linked monomers can be selected with regard to the othermonomers of the conductive polymer such that the conductive polymer canhave suitable solubility in water or other aqueous solvent. Theselection of monomer types, amounts, or ratios can also be determinedregarding the amount of hydrophilic surface molecules on thenanoparticles.

FIG. 1A illustrates a method of preparing an example of a conductivepolymer 10. As shown, a random copolymer comprising3,4-ethylenedioxythiophene and thiol-substituted alkylthiophenes asrepeating units was prepared in choloroform solvent using FeCl₃ throughan oxidative coupling reaction. To prepare metal nanoparticlessurrounded by hydrophilic moieties, the method of Schiffrin (Brust etal., J. Chem. Soc., Chem. Commun., 801 (1994)) was modified forpreparing gold nanoparticles capped with linear alkanethiols by reducingHAuCl₄ using sodium citrate in the presence of a mixture of ethyleneoxide substituted with thiol and the above resulting copolymer. Theresultant product is a polymer 10 having a conductive monomer 12 and amonomer 14 coupled to a nanoparticle 16, where the nanoparticle 16 hasfrom 0 to a desired number of hydrophilic moieties 18.

Alternatively, the reaction can be as follows: providing3,4-ethylenedioxythiophene and alkylthiophene monomers; providing ananoparticle having hydrophilic moieties as well as being linked to thealkylthiophene monomer; and polymerizing the 3,4-ethylenedioxythiophene,alkylthiophene, and nanoparticle monomers. In another alternative, thereaction can be as follows: providing 3,4-ethylenedioxythiophene andalkylthiophene monomers; providing a nanoparticle linked to a monomer;and polymerizing the 3,4-ethylenedioxythiophene, alkylthiophene, andnanoparticle monomers. Any hydrophilic moieties can be linked to thenanoparticle before, during or after polymerization. Thus, any methodthat can be performed to prepare a conductive polymer having aconductive nanoparticle can be utilized, and method steps can beperformed in various orders and at different times and may result indifferent intermediate products.

In one embodiment, the nanoparticle can be coupled to the monomer 14through a linker 17. The linker can be an alkyl spacer that can link amonomer to a nanoparticle. For example, the linker can be coupled to theparticle through a terminal thiol group, such as butanethiol,pentanethiol, hexanethiol, and heptanethiol.

For example, 3,4-ethylenedioxythiophene and a thiol-substitutedalkylthiophene, can be copolymerized together by an oxidative couplingreaction. The copolymer can contain a monomer photoreactive group.Optionally, 10% or less composition of photoreactive monomer can beuseful and retain electrical conductivity.

When including the alkylthiophene monomeric unit in the copolymer, theelectrical conductivity can be reduced to some extent. However, theratio and amount of monomers can be optimized for improving solubilityin aqueous or polar, aprotic solvent system for being deposited as anelectrically conductive layer. For example, the amount of gold can be afactor to modulate in order to control the conductivity of the resultantmatrices.

FIG. 1B shows a conductive polymer 10 where the nanoparticle 16 does notinclude a hydrophilic moiety.

FIG. 1C shows a conductive polymer where a portion of nanoparticles(“n”) have a hydrophilic moiety and a portion of the nanoparticles (“n”)can be devoid of any hydrophilic moiety.

In one embodiment, the ratio of conductive monomers linked to thenanoparticle can be tuned for optimizing electrical conductivity as wellas solubility in aqueous solvent or water, and each monomer can beindividually selected and optimized.

In one embodiment, one of the polymers of FIGS. 1A-1C can be prepared toinclude hydrophobic moieties in place of the hydrophilic moieties. Also,the hydrophilic moieties can be substituted with amphiphilic,amphipathic, or amphoteric moieties. These moieties can be useful forproviding solubility or the capability of being suspended in mixedsolvents or organic solvents, as well as other systems.

Additionally, the monomer 14 that is coupled to the nanoparticle 16 canbe a conductive monomer.

In one embodiment, the amount or ratio of monomers having a conductivenanoparticle can be modulated to increase electrical conductivity, whichcan include an increase in conductivity compared to a conductive polymerthat is devoid of conductive nanoparticle-containing monomers.

The conductive polymer can be used for preparing a polymer producthaving a large area of deposition. This can be useful for preparingfilms, sheets, rolls, plates, coatings, circuit paths, or otherconductive polymeric configuration. The conductive polymer can beprepared into a transparent conducting film or coating, and can beapplied by a surface treatment or blending to prepare the conductivepolymers having a conductive nanoparticle-containing monomer. Forexample, a wet processing technique with the conductive monomers andnanoparticle-containing monomers can be used for achieving a largecoated area or large film size.

The conductive polymers can be used to prepare ordered or disorderednanostructures. The conductive polymers can also be used in applicationsfor constructing improved transparent conducting films bearingconductive nanoparticles.

In one embodiment, an electrically conductive polymer can include atleast one monomer that is linked to a conductive nanoparticle. Thepolymer may have other conductive monomers. For example, theelectrically conductive polymer can include a combination of conductivemonomers and monomers linked to conductive nanoparticles.

In one embodiment, the electrically conductive polymers can have metalnanoparticles. The metal nanoparticles can be surrounded by hydrophilicmoieties. The hydrophilic moieties can be modulated in order to optimizethe formation of a conducting channel, or use in tailoring a nonuniformarrangement of the ionic polymers in the ionic complex. Furthermore, theelectrically conductive polymers can be dissolved in an aqueous solutionsuch as water, alcohol and the like. The solubility property allows theelectrically conductive polymers to be easily used in wet processing.

In one embodiment, an electrically conductive polymer can be a polymerhaving a monomer of Formula 1 and a monomer of Formula 2. The polymercan be a block copolymer with two or more monomers of Formula 1 being ina sequence and two or more monomers of Formula 2 being in a sequence.The copolymer can also include the monomers of Formulas 1 and 2alternating in an ordered sequence or in a random distribution or anyother copolymer configuration. Generally, A can be a conductive monomerand B can be a conductive monomer linked to a conductive nanoparticle.

In one embodiment, the electrically conductive polymer can include themonomers of formulas 1 and 2 as described below:

In Formulas 1 and 2, A and B can be independently selected from thegroup of phenylene, phenylene vinylene, pyrrolylene, pyrrolylenevinylene, thienylene, thienylene vinylene, fluorenylene, fluorenylenevinylene, furanylene, furanylene vinylene, phenothiazinylene,phenothiazinylene vinylene, phenazinylene, phenazinylene vinylene,phenoxazinylene and phenoxazinylene vinylene, which are unsubstituted orsubstituted with one or more substituents. The conductive polymer caninclude one or more B monomers having one or more R1 groups. The R₁ isL-G, wherein G is a conductive nanoparticle (optionally with hydrophilicmoieties) and L is a linker or a bond. Also, the B monomer and/or R1 caninclude, a hydroxyl, alkyl, alkenyl, alkynyl, alkanoyl, alkanoylamino,alkenoyl, alkynoyl, alkoxy, alkoxycarbonyl, alkoxycarbonylamino,alkylamino, alkylaminocarbonyl, dialkylaminocarbonyl, alkylsulfonyl,alkylsulfinyl, sulfonylaminoalkyl, alkylsulfonylaminocarbonyl,aminoalkyl, cyanoalkyl, halogen, haloalkyl, haloalkenyl, haloalkynyl,haloalkanoyl, haloalkenoyl, haloalkynoyl, haloalkoxy,haloalkoxycarbonyl, hydroxyalkyl, oxoalkyl, cycloalkyl, cycloalkenyl,cycloalkanoyl, cycloalkenoyl, cycloalkoxy, cycloalkoxycarbonyl, aryl,arylene, heterocycle, heterocyclyl, heteroaryl, heteroarylene,arylalkyl, heteroarylalkyl, arylalkanoyl, heteroarylalkanoyl,arylalkenoyl, heteroarylalkenoyl, arylalkynoyl, heteroarylalkynoyl,arylalkoxy, heteroarylalkoxy, aryloxy, heteroaryloxy, aryloxycarbonyl,heteroarylxoycarbonyl, arylalkoxycarbonyl, heteroarylalkoxycarbonyl,alkylthio, alkylthioalkyl, arylthio, arylsulfonyl and arylsulfinyl; orthe substituent may form a 3, 4, 5, 6, or 7-membered aromatic oralicyclic ring, and the ring may optionally include one or more divalentnitrogen, sulfur or oxygen atoms; and the substituents may be furthersubstituted or unsubstituted, branched or unbranched and linear,branched or cyclic.

The conductive polymer may have a degree of polymerization of 100 to1,000.

In the above Formulas 1 and 2, A and B are not limited to theexemplified monomers, and any monomer consisting of well-knownelectrically conductive polymers can be used. The monomer of Formula 1and the monomer of Formula 2 may be easily dissolved in aqueous solvent.In one embodiment, the conductive polymer can be either undoped or dopedwith at least one monomer acid or a polymer acid. The monomer or polymeracid can be included in the polymer chain or within the polymercomposition.

In one embodiment, the conductive nanoparticle can be incorporated intomonomer B using a linker. The linker can be an alkyl or the like. Thebinding of the nanoparticle to monomer B can be performed using anywell-known method in the art.

In one embodiment, the conductive polymer can include a monomer selectedfrom the monomers of Formulas 3-5. Also, either Formula 1 or Formula 2above can be one of the monomers of Formulas 3-5. The monomers ofFormulas 3-5 can be as described below:

In Formulas 3-5, X₁, X₂ and X₃ can be independently NH, O, S or PH.

In Formulas 3-5, R₂ and R₂′, R₃ and R₃′, R₄ and R₄′ can be independentlyselected from the group consisting of hydrogen, hydroxyl, alkyl,alkenyl, alkynyl, alkanoyl, alkanoylamino, alkenoyl, alkynoyl, alkoxy,alkoxycarbonyl, alkoxycarbonylamino, alkylamino, alkylaminocarbonyl,dialkylaminocarbonyl, alkylsulfonyl, alkylsulfinyl, sulfonylaminoalkyl,alkylsulfonylaminocarbonyl, aminoalkyl, cyanoalkyl, halogen, haloalkyl,haloalkenyl, haloalkynyl, haloalkanoyl, haloalkenoyl, haloalkynoyl,haloalkoxy, haloalkoxycarbonyl, hydroxyalkyl, oxoalkyl, cycloalkyl,cycloalkenyl, cycloalkanoyl, cycloalkenoyl, cycloalkoxy,cycloalkoxycarbonyl, aryl, arylene, heterocycle, heterocyclyl,heteroaryl, heteroarylene, arylalkyl, heteroarylalkyl, arylalkanoyl,heteroarylalkanoyl, arylalkenoyl, heteroarylalkenoyl, arylalkynoyl,heteroarylalkynoyl, arylalkoxy, heteroarylalkoxy, aryloxy,heteroaryloxy, aryloxycarbonyl, heteroaryloxycarbonyl,arylalkoxycarbonyl, heteroarylalkoxycarbonyl, alkylthio, alkylthioalkyl,arylthio, arylsulfonyl and arylsulfinyl; or, R₂ and R₂′, R₃ and R₃′, R₄and R₄′ together may form an alkylene or alkenylene chain completing a3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, and the ring mayoptionally include one or more divalent nitrogen, sulfur or oxygenatoms; and the substituents may be further substituted or unsubstituted.As an example of a ring, the substitutents R₂ and R₂′, R₃ and R₃′, R₄and R₄′ together can form a ring such as ProDOT(3,4-Propylenedioxythiophene).

In one embodiment, one or more of R₂, R₂′, R₃, R₃′, R₄, and R₄′ can beL-G, where G can be a nanoparticle, such as a metal nanoparticle with orwithout hydrophilic moieties. The L can be selected from the group ofalkylthio, alkenylthio, alkynylthio, and alkoxythio, which isunsubstituted or substituted, branched or unbranched and linear,branched or cyclic. The alkyl portion can be as described herein. In oneembodiment, G is a metal nanoparticle with hydrophilic moieties, wherethe hydrophilic moiety can be represented by Formula 6.

In Formula 6, R₅, R₆ and R₇ can be independently hydrogen, hydroxyl,alkyl, or Formula 7. In Formula 7, Q represents alkylene having one ormore carbons, d is a number, and R₈ is carboxylic acid, sulfonic acid,or a straight or branched alkyl, which is substituted with thiol.Generally, Q can be an alkylene having one or two carbons where Formula7 is water soluble. d can be 1 to 3.

In one embodiment, at least one of R₅, R₆ and R₇ is Formula 7.

In one embodiment, R₈ may be a C₁₋₁₈ alkylthio, for example, ethylthio,propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio,nonylthio, dodecylthio, hexadecylthio, octadecylthio, or the like.

In one embodiment, the hydrophilic moiety can be ammonium salt.

In one embodiment, conductive polymer may be doped with a polymeric acidthrough an ionic bond. Any polymeric acids can be doped into theconductive polymer so long as the polymeric acids do not reduce thesolubility of the conductive polymer to an amount that the conductivepolymer is no longer soluble or workable.

The polymeric acids can be used for providing charges on the conductivepolymer to elevate electrical conductivity. Such polymeric acidsincludes poly(styrenesulfonate) and others.

In one embodiment, G may be a metal nanoparticle, and the metal isselected from the group consisting of gold, silver, copper and platinum,which have high conductivity. Methods of making metal nanoparticles arewell-known in the art. See, e.g., Schmid, G. (ed.) Clusters and Colloids(VCH, Weinheim, 1994); Hayat, M. A. (ed.) Colloidal Gold: Principles,Methods, and Applications (Academic Press, San Diego, 1991); Massart,R., IEEE Transactions On Magnetics, 17, 1247 (1981); Ahmadi, T. S. etal., Science, 272, 1924 (1996); Henglein, A. et al., J. Phys. Chem., 99,14129 (1995); Curtis, A. C., et al., Angew. Chem., Int. Ed. Engl., 27,1530 (1988); Brust et al., J. Chem. Soc., Chem. Commun., 801 (1994); PCTapplication WO 98/21587. Suitable nanoparticles are also commerciallyavailable from, e.g., Ted Pella, Inc., Amersham Corporation, Nanoprobes,Inc., BBI, Bangs Laboratories, etc.

In one embodiment, the conductive polymer of the present disclosure maycomprise a monomer having a photoreactive group in the side chain. Thephotoreactive group induces a photocrosslinking reaction between thephotoreactive groups in the copolymers. The kinds of photoreactivegroups are not limited. Any conventional photoreactive group can beincorporated into the copolymer.

Such a photoreactive group may be selected from the group consisting ofa cinnamoyl group, a chalcone group, a coumarin group, a maleimidegroup, an anthracenic group and a pyrimidine group, which isunsubstituted or substituted with at least one substituent having atleast one ionic moiety. When the photoreactive group is substituted withat least one substituent having at least one ionic moiety, the ionicmoiety can allow the electrically conductive polymer to sustain moresolubility in aqueous solvent. The photoreactive group can be selecteddepending on hardening conditions. For example, a cinnamoyl group can becrosslinked under 254 nm UV light. Chalcone can be cured under 365 nmlight at room temperature and ambient conditions. Therefore, a skilledartisan can consider the hardening condition of a conductive layer andselect the proper photoreactive group to be used in the presentcopolymer composition.

The electrically conductive polymer in the present disclosure can beprepared by conventional methods well-known in the art. In the presentdisclosure, the copolymer can be prepared by copolymerizing Formulas 1and 2, and then introducing the metal nanoparticles to B. Thecopolymerization can be performed, for example, through an oxidativecoupling reaction, or other polymerization.

Introduction of metal nanoparticles into the polymer can besimultaneously achieved during polymerization when a monomer includes afree thiol group that can react with the nanoparticle. For example, agold nanoparticles can be synthesized by reducing HAuCl₄ with a reducingagent such as sodium citrate, H₂O₂, NaBH₄, or the like. Also,hydrophillic moieties such as thiol terminated alkylene oxides can bealso added to the reaction mixture to make the metal nanoparticles besurrounded by the hydrophilic moieties.

In one embodiment, the conductive polymer can have any percentage of themonomers being linked to a conductive polymer such that electricalconductance is maintained or increased. For example, from 1% to 90% ofthe monomers can have a conductive nanoparticle, or less than 80%, lessthan 70%, less than 60%, less than 50%, less than 40%, less than 30%,less than 20% or less than 10%. In another example, a composition of 10%or less of monomers having metal nanoparticles can provide electricalconductivity.

In one embodiment, the ratio of conductive monomer units and monomerunits linked to a nanoparticle may be from 1:0.01 to 1:10, 1:0.5 to 1:5.Once the conductive polymer is prepared, electrical conductivity andsolubility can be quickly checked after synthesis to adjust for theproper ratio of m and n. The ratio of m and n may be adjusted tooptimize electrical conductivity and solubility in an aqueous or polar,aprotic solvent system. The amount of metal nanoparticles can be afactor to control the conductivity of the resultant matrices.

In one embodiment, a composition having a conductive polymer with aconductive nanoparticle, where the composition can be in various formatsand configurations, such as a film or layer. To fabricate a conductivefilm or layer using a conductive polymer with conductive nanoparticles,the conductive polymer with conductive nanoparticles can be dispersed ina solvent to prepare a composition. Any solvent can be used for theconductive copolymer composition so long as it can substantiallydissolve the conductive copolymer. Exemplary solvents useful in thepresent disclosure can be selected from water, alcohol, or mixturesthereof. In some instances organic solvents can be used, such as whenthe nanoparticle is associated with hydrophobic-containing moieties.

The composition may further include other water soluble or dispersiblematerials. Depending on the final application of the conductive polymer,examples of types of additional water soluble or dispersible materialswhich can be added include, but are not limited to, polymers, dyes,coating aids, carbon nanotubes, metal nanowires and nanoparticles,organic and inorganic conductive inks and pastes, charge transportmaterials, piezoelectric, pyroelectric, or ferroelectric oxidenano-particles or polymers, photoconductive oxide nanoparticles orpolymers, dispersing agents, and combinations thereof. The materials canbe simple molecules or polymers. Examples of other suitable watersoluble or dispersible polymers include, but are not limited to,polyacrylamide, polyvinylalcohol, poly(2-vinylpridine),poly(vinylacetate), poly(vinylmethylether), poly(vinylpyrrolidone),poly(vinylbutyral), poly(styrenesulfonic acid), and conductive polymerssuch as polythiophenes, polyanilines, polyamines, polypyrroles,polyacetylenes, and combinations thereof.

In one embodiment, the conductive polymer having conductivenanoparticles can be formed into a conductive layer or film.

The term “layer” or “film” refers to a coating covering a desired areaand may be used interchangeably. The area can be as large as an entiredevice or as small as a specific functional area such as the actualvisual display, or even as small as a single sub-pixel. Films can beformed by any conventional deposition technique, including vapordeposition and liquid deposition. However, considering the solubility ofthe present conductive polymer in aqueous solution, liquid depositioncan provide more convenience and enable a large patterned layer or filmto be fabricated. The patterns can be formed into electronic paths.Typical liquid deposition techniques include, but are not limited to,continuous deposition techniques such as spin coating, gravure coating,curtain coating, dip coating, slot-die coating, spray coating,continuous nozzle coating, and doctor blade coating; and discontinuousdeposition techniques such as ink-jet printing, gravure printing, andscreen printing.

The conductive polymer can be used as an electrode or an electrodebuffer layer to increase quantum efficiency. In an organic transistor,the conductive polymer can be used as an electrode material for a gate,a source-drain electrode, and the like. Further, in an electronicdevice, the conductive polymer compositions can be deposited to formbuffer layers. The term “buffer layer” as used herein is intended tomean an electrically conductive or semiconductive layer which can beused between an anode and an active organic material. A buffer layer isbelieved to accomplish one or more functions in an organic electronicdevice, including, but not limited to, planarization of the underlyinglayer, hole transport, hole injection, scavenging of impurities such asoxygen and metal ions, among other aspects to facilitate or to improvethe performance of an organic electronic device.

In one embodiment, an article can be prepared to include at least oneelectrically conductive layer formed from the conductive polymercomposition. For example, organic electronic devices that may benefitfrom having one or more layers made from the composition include, butare not limited to, (1) devices that convert electrical energy intoradiation (e. g., a light-emitting diode, light emitting diode displays,liquid crystal displays, electronic paper, touchscreens, or diodelasers), (2) devices that detect signals through electronics processes(e. g., photodetectors, photoconductive cells, photoresistors,photoswitches, phototransistors, phototubes, IR detectors), (3) devicesthat convert radiation into electrical energy, (e.g., a photovoltaicdevice or solar cell), and (4) devices that include one or moreelectronic components that include one or more organic semi-conductorlayers (e. g., a transistor or diode). Other uses for the compositionsinclude coating materials for memory storage devices, antistatic films,biosensors, electrochromic devices, solid electrolyte capacitors, energystorage devices such as a rechargeable battery, electromagnetic waveshielding films, window de-icers, heat reflectors, and architecturalmaterials. As mentioned above, the conductivity of an electricallyconductive layer or film can be tuned. If the layers or films have highconductivity, they can be used for OLEDs, solar cells, LCDs and thelike. On the other hand, if layers or films have low conductivity, theycan be used for electro-optic modulators, microresonators,interferometers, optical switches, directional couplers, multiplexersand the like.

As an example, an organic electroluminescent device can be prepared froma composition having a conducting polymer. The present disclosure willbe further made clear from the following example described in detail.However, it is to be understood that the present disclosure is notlimited thereto, and may be otherwise variously embodied and practiced.

The monomer can be linked to the conductive nanoparticle by a variety ofchemical linkages. For example, the monomer can include a moiety thatcan react with the conductive nanoparticle, where such a moiety may be,but not limited to, thiol (HS), carboxy (COOH), hydroxy (OH), cyano(CN), a halogen, an alkyl substituted with a halogen, and the like. Whenthe core is a metal or alloy material, such as gold (Au), silver (Ag),copper (Cu) or palladium (Pd), Q may be a thiol (SH) or cyano group(CN).

Those of ordinary skill in the art will appreciate that, for this andother processes and methods disclosed herein, the functions performed inthe processes and methods may be implemented in differing order.Furthermore, the outlined steps and operations are provided only asexamples, and some of the steps and operations may be optional, combinedinto fewer steps and operations, or expanded to include additional stepsand operations without detracting from the essence of the presentdisclosure.

EXAMPLES

In order to prepare a random copolymer, thiol-substitutedalkylthiophenes are prepared, and then copolymerized with3,4-ethylenedioxythiophene in choloroform solvent using FeCl₃ through anoxidative coupling reaction. The resulting copolymers are dissolved inwater to prepare a homogeneous solution, and polystyrene sulfonatesodium is added and reacted for about 1-3 hrs in the solution to preparea electrically conductive polymer doped with PSS.

To prepare metal nanoparticles surrounded by hydrophilic moieties, themethod of Schiffrin (Brust et al., J. Chem. Soc., Chem. Commun., 801(1994)) was modified for preparing gold nanoparticles capped with linearalkanethiols by reducing HAuCl₄ using sodium citrate in the presence ofa mixture of ethylene oxide substituted with thiol and the aboveresulting copolymer, to yield copolymers having gold nanoparticlessurrounded by hydrophilic ethylene oxide moieties. The resultingcopolymers have enhanced electrical conductivity.

The copolymer composition is used as an electrode of a flexible displaydevice. The flexible display device generally include an anode layer, ahole injection layer, an electroluminescent layer, a cathode layer, anda flexible organic film. A transparent plastic substrate having goodmanageability and waterproofness may used as the flexible organic filmlike polycarbonate, polyethylene terephthalate (PET) or polyethylenenaphthalate(PEN).

The flexible display device can be manufactured using a typical methodof preparing display devices, which are not particularly limited. First,an anode layer or cathode layer as a first electrode is formed on theplastic substrate. The first electrode layer is formed by spin coatingthe above copolymer composition on the plastic substrate.

The hole injection layer is formed on the first electrode. The formationof the hole injection layer reduces contact resistance of the firstelectrode and the electroluminescent layer and improves the electrontransport ability of the first electrode to the electroluminescentlayer, thereby improving the driving voltage and the lifetime of theelectroluminescent device.

The hole injection layer (also referred to as the buffer layer) isformed by spin coating on the first electrode and drying it. Typicalconducting polymers employed as buffer layers include polyaniline andpolydioxythiophenes such as poly(3,4-ethylenedioxythiophene) (PEDOT).These materials can be prepared by polymerizing aniline ordioxythiophene monomers in aqueous solution in the presence of a watersoluble polymeric acid, such as poly(styrenesulfonic acid) (PSSA), orpoly(2-acrylamido-2-methyl-1-propanesulfonic acid) (“PAAMP SA”), asdescribed in, for example, U.S. Pat. No. 5,300,575 and published in PCTapplication WO 02/065484. A well known PEDOT/PSS material is Baytron®-P,commercially available from H. C. Starck, GmbH (Leverkusen, Germany).

The electroluminescent layer is formed on the hole injection layer. Amaterial for the electroluminescent layer is not particularly limited,but examples thereof include oxadiazole dimer dyes (Bis-DAPDXP), spirocompounds (Spiro-DPVBi, Spiro-6P), triarylamine compounds,bis(styryl)amine (DPVBi, DSA), Flrpic, CzTT, Anthracene, TPB, PPCP, DST,TPA, OXD-4, BBOT, AZM-Zn, etc. which are blue materials, Coumarin 6,C545T, Quinacridone, Ir(ppy)₃, etc., which are green materials, andDCM1, DCM2, Eu(thenoyltrifluoroacetone)₃(Eu(TTA)₃),butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB), etc.,which are red materials. In addition, examples of the polymerlight-emitting material include polymers such as phenylene, phenylenevinylene, thiophene, fluorene, and spiro-fluorene-based polymers andaromatic compounds containing nitrogen, but are not limited thereto.

The electroluminescent layer forming composition further includes adopant, if necessary. The amount of the dopant varies depending on thematerial for the electroluminescent layer, but may be generally 30-80parts by weight based on 100 parts by weight of a material for theelectroluminescent layer (total weight of the host and the dopant). Whenthe amount of the dopant is not within this range, the luminouscharacteristics of an electroluminescent display device are reduced.Examples of the dopant include arylamine, perylenes, pyrroles,hydrazones, carbazoles, stilbenes, starburstes, oxadiazoles andderivatives thereof.

The hole transport layer may be optionally formed between the holeinjection layer and the electroluminescent layer.

The material for the hole transport layer is not particularly limited,but may be selected from a compound having a carbazole group and/or anarylamine group, which transport electrons, a phthalocyanine-basedcompound, and a triphenylene derivative. More particularly, the electrontransport layer (HTL) may be composed of at least one material selectedfrom the group consisting of 1,3,5-tricarbazolylbenzene,4,4′-biscarbazolylbiphenyl, polyvinylcarbazole, m-biscarbazolylbenzene,4,4′-biscarbazolyl-2,2′-dimethylbiphenyl,4,4′,4″-tri(N-carbazolyl)triphenylamine,1,3,5-tri(2-carbazolylphenyl)benzene,1,3,5-tris(2-carbazolyl-5-methoxyphenyl)benzene,bis(4-carbazolylphenyl)silane,N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine(TPD), N,N′-di(naphthalene-1-yl)-N,N′-diphenyl benzidine (α-NPD),N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB),IDE320 (Idemitsu Kosan Co., LTD.),poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine (TFB), andpoly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB),but are not limited thereto. The hole blocking layer may be composed ofphenanthrolines (e.g., BCP available from UDC), imidazoles, triazoles,oxadiazoles (e.g., PBD), aluminium complex (available from UDC), or BAlqand the like.

Then, the second electrode is formed on the resultant and sealed tocomplete an organic electroluminescent device. The material for thesecond electrode is not particularly limited, but may be a metal havinga low work function, i.e., Li, Cs, Ba, Ca, Ca/Al, LiF/Ca, LiF/Al,BaF₂/Ca, Mg, Ag, Al, or an alloy thereof, or a multilayer thereof.

The organic electroluminescent device of the present disclosure does notrequire a particular apparatus or method for manufacturing it, and canbe manufactured using a conventional manufacturing method.

The present disclosure is not to be limited in terms of the particularexamples described in this disclosure. Many modifications and variationscan be made without departing from its spirit and scope, as will beapparent to those skilled in the art. Functionally equivalent methodsand apparatuses within the scope of the disclosure, in addition to thoseenumerated herein, will be apparent to those skilled in the art from theforegoing descriptions. Such modifications and variations are intendedto fall within the scope of the appended claims. The present disclosureis to be limited only by the terms of the appended claims, along withthe full scope of equivalents to which such claims are entitled. It isto be understood that this disclosure is not limited to particularmethods, reagents, compounds, or compositions, which can, of course,vary. It is also to be understood that the terminology used herein isfor the purpose of describing particular examples only, and is notintended to be limiting.

Unless otherwise indicated, this disclosure uses the definitionsprovided below. Some of the definitions and formulae may include a dash(“-”) to indicate a bond between atoms or a point of attachment to anamed or unnamed atom or group of atoms. Other definitions and formulaemay include an equal sign (“=”) or an identity symbol (“≡”) to indicatea double bond or a triple bond, respectively.

“Substituted” groups are those in which one or more hydrogen atoms havebeen replaced with one or more non-hydrogen groups, provided thatvalence requirements are met and that a chemically stable compoundresults from the substitution.

“Alkyl” refers to straight chain and branched saturated hydrocarbongroups, generally having a specified number of carbon atoms (i. e., C₁₋₆alkyl refers to an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atomsand C₁₋₁₂ alkyl refers to an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8,9, 10, 11, or 12 carbon atoms). Examples of alkyl groups include,without limitation, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl,i-butyl, t-butyl, pent-1-yl, pent-2-yl, pent-3-yl, 3-methylbut-1-yl,3-methylbut-2-yl, 2-methylbut-2-yl, 2,2,2-trimethyleth-1-yl, n-hexyl,and the like. Alkyls can also be cyclic.

The terms aliphatic or alkyl also encompasses alkenyl groups, such asvinyl, allyl, aralkyl and alkynyl groups.

Substitutions within an alkyl or aliphatic group can include any atom orgroup that can be tolerated in the aliphatic moiety, including but notlimited to halogens, sulfurs, thiols, thioethers, thioesters, amines(primary, secondary, or tertiary), amides, ethers, esters, alcohols,oxygen, and the like. The aliphatic groups can by way of example alsoinclude modifications such as azo groups, keto groups, aldehyde groups,carbonyl groups, carboxyl groups, nitro, nitroso or nitrile groups,heterocycles such as imidazole, hydrazino or hydroxylamino groups,isocyanate or cyanate groups, and sulfur containing groups such assulfoxide, sulfone, sulfide, and disulfide. Additionally, thesubstitutions can be via single, double, or triple bonds, when relevantor possible.

Further, alkyl groups may also contain hetero substitutions, which aresubstitutions of carbon atoms, by hetero atoms such as, for example,nitrogen, oxygen, phosphorous, or sulfur. As such, a linker comprised ofa substituted aliphatic can have a backbone comprised of carbon,nitrogen, oxygen, sulfur, phosphorous, and/or the like. Heterocyclicsubstitutions refer to alkyl rings having one or more hetero atoms.Examples of heterocyclic moieties include but are not limited tomorpholino, imidazole, tetrahydrofuran, and pyrrolidino.

“Alkylene” refers to a linear or branched saturated divalent hydrocarbonradical. Examples of the alkylene group include, without limitation,methylene, ethylene, propylene, butylenes, and the like.

“Heteroalkylene” refers to an alkylene chain as described above, inwhich one or more C-atoms have in each case been replaced by aheteroatom mutually independently selected from the group comprisingoxygen, sulfur and nitrogen (NH). Heteroalkylene groups can have 1, 2 or3 heteroatom(s), particularly one heteroatom, selected from the groupcomprising oxygen, sulfur and nitrogen (NH) as the chain member(s).Heteroalkylene groups can be 2- to 20 membered or 2- to 12-membered,particularly 2- to 6-membered, and more particularly 2- or 3-membered.Any alkylene can be a heteroalkylene.

“Alkenyl” refers to straight chain and branched hydrocarbon groupshaving one or more unsaturated carbon-carbon bonds, and generally havinga specified number of carbon atoms. Examples of alkenyl groups include,without limitation, ethenyl, 1-propen-1-yl, 1-propen-2-yl,2-propen-1-yl, 1-buten-1-yl, 1-buten-2-yl, 3-buten-1-yl, 3-buten-2-yl,2-buten-1-yl, 2-buten-2-yl, 2-methyl-1-propen-1-yl,2-methyl-2-propen-1-yl, 1,3-butadien-1-yl, 1,3-butadien-2-yl, and thelike.

“Alkynyl” refers to straight chain or branched hydrocarbon groups havingone or more triple carbon-carbon bonds, and generally having a specifiednumber of carbon atoms.

Examples of alkynyl groups include, without limitation, ethynyl,1-propyn-1-yl, 2-propyn-1-yl, 1-butyn-1-yl, 3-butyn-1-yl, 3-butyn-2-yl,2-butyn-1-yl, and the like.

“Alkanoyl” and “alkanoylamino” refer, respectively, to alkyl-C(O)— andalkyl-C(O)—NH—, where alkyl is defined above, and generally includes aspecified number of carbon atoms, including the carbonyl carbon.Examples of alkanoyl groups include, without limitation, formyl, acetyl,propionyl, butyryl, pentanoyl, hexanoyl, and the like.

“Alkenoyl” and “alkynoyl” refer, respectively, to alkenyl-C(O)— andalkynyl-C(O)—, where alkenyl and alkynyl are defined above. Referencesto alkenoyl and alkynoyl generally include a specified number of carbonatoms, excluding the carbonyl carbon. Examples of alkenoyl groupsinclude, without limitation, propenoyl, 2-methylpropenoyl, 2-butenoyl,3-butenoyl, 2-methyl-2-butenoyl, 2-methyl-3-butenoyl,3-methyl-3-butenoyl, 2-pentenoyl, 3-pentenoyl, 4-pentenoyl, and thelike. Examples of alkynoyl groups include, without limitation,propynoyl, 2-butynoyl, 3-butynoyl, 2-pentynoyl, 3-pentynoyl,4-pentynoyl, and the like.

“Alkoxy,” “alkoxycarbonyl,” and “alkoxycarbonylamino,” refer,respectively, to alkyl-O—, alkenyl-O, and alkynyl-O; to alkyl-O—C(O)—,alkynyl-O—C(O)—; and to alkyl-O—C(O)—NH—, and alkynyl-O—C(O)—NH—, wherealkyl, alkenyl, and alkynyl are defined above. Examples of alkoxy groupsinclude, without limitation, methoxy, ethoxy, n-propoxy, i-propoxy,n-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, and the like.Examples of alkoxycarbonyl groups include, without limitation,methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl,n-butoxycarbonyl, s-butoxycarbonyl, t-butoxycarbonyl, n-pentoxycarbonyl,s-pentoxycarbonyl, and the like.

“Alkylamino,” “alkylaminocarbonyl,” “dialkylaminocarbonyl,”“alkylsulfonyl,” “alkylsulfinyl,” “sulfonylaminoalkyl,” and“alkylsulfonylaminocarbonyl” refer, respectively, to alkyl-NH—,alkyl-NH—C(O)—, alkyl₂-N—C(O)—, alkyl-S(O₂)—, alkyl-S(═O)—,HS(O₂)—NH-alkyl-, and alkyl-S(O)—NH—C(O)—, where alkyl is defined above.

“Aminoalkyl” and “cyanoalkyl” refer, respectively, to NH₂-alkyl andN═C-alkyl, where alkyl is defined above.

“Halo,” “halogen” and “halogeno” may be used interchangeably, and referto fluoro, chloro, bromo, and iodo.

“Haloalkyl,” “haloalkenyl,” “haloalkynyl,” “haloalkanoyl,”“haloalkenoyl,” “haloalkynoyl,” “haloalkoxy,” and “haloalkoxycarbonyl”refer, respectively, to alkyl, alkenyl, alkynyl, alkanoyl, alkenoyl,alkynoyl, alkoxy, and alkoxycarbonyl groups substituted with one or morehalogen atoms, where alkyl, alkenyl, alkynyl, alkanoyl, alkenoyl,alkynoyl, alkoxy, and alkoxycarbonyl are defined above. Examples ofhaloalkyl groups include, without limitation, trifluoromethyl,trichloromethyl, pentafluoroethyl, pentachloroethyl, and the like.

“Hydroxyalkyl” and “oxoalkyl” refer, respectively, to HO-alkyl andO=alkyl, where alkyl is defined above. Examples of hydroxyalkyl andoxoalkyl groups include, without limitation, hydroxymethyl,hydroxyethyl, 3-hydroxypropyl, oxomethyl, oxoethyl, 3-oxopropyl, and thelike.

“Cycloalkyl” refers to saturated monocyclic and bicyclic hydrocarbonrings, generally having a specified number of carbon atoms that comprisethe ring (i.e., C3-7 cycloalkyl refers to a cycloalkyl group having 3,4, 5, 6 or 7 carbon atoms as ring members). The cycloalkyl may beattached to a parent group or to a substituent at any ring atom, unlesssuch attachment would violate valence requirements. Likewise, thecycloalkyl groups may include one or more non-hydrogen substituentsunless such substitution would violate valence requirements.

Examples of monocyclic cycloalkyl groups include, without limitation,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Examplesof bicyclic cycloalkyl groups include, without limitation,bicyclo[1.1.0]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.1.0]pentyl,bicyclo[2.1.1]hexyl, bicyclo[3.1.0]hexyl, bicyclo[2.2.1]heptyl,bicyclo[3.2.0]heptyl, bicyclo[3.1.1]heptyl, bicyclo[4.1.0]heptyl,bicyclo[2.2.2]octyl, bicyclo[3.2.1]octyl, bicyclo[4.1.1]octyl,bicyclo[3.3.0]octyl, bicyclo[4.2.0]octyl, bicyclo[3.3.1]nonyl,bicyclo[4.2.1]nonyl, bicyclo[4.3.0]nonyl, bicyclo[3.3.2]decyl,bicyclo[4.2.2]decyl, bicyclo[4.3.1]decyl, bicyclo[4.4.0]decyl,bicyclo[3.3.3]undecyl, bicyclo[4.3.2]undecyl, bicyclo[4.3.3]dodecyl, andthe like, which may be attached to a parent group or a substituent atany of the ring atoms, unless such attachment would violate valencerequirements.

“Cycloalkenyl” refers to monocyclic and bicyclic hydrocarbon ringshaving one or more unsaturated carbon-carbon bonds and generally havinga specified number of carbon atoms that comprise the ring (i.e., C3-7cycloalkenyl refers to a cycloalkenyl group having 3, 4, 5, 6 or 7carbon atoms as ring members). The cycloalkenyl may be attached to aparent group or to a subsituent at any ring atom, unless such attachmentwould violate valence requirements.

Likewise, the cycloalkenyl groups may include one or more non-hydrogensubstituents unless such substitution would violate valencerequirements. Useful substituents include, without limitation, alkyl,alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy,alkoxycarbonyl, alkanoyl, and halo, as defined above, and hydroxy,mercapto, nitro, and amino.

“Cycloalkanoyl” and “cycloalkenoyl” refer to cycloalkyl-C(O)— andcycloalkenyl-C(O)—, respectively, where cycloalkyl and cycloalkenyl aredefined above. References to cycloalkanoyl and cycloalkenoyl generallyinclude a specified number of carbon atoms, excluding the carbonylcarbon. Examples of cycloalkanoyl groups include, without limitation,cyclopropanoyl, cyclobutanoyl, cyclopentanoyl, cyclohexanoyl,cycloheptanoyl, 1-cyclobutenoyl, 2-cyclobutenoyl, 1-cyclopentenoyl,2-cyclopentenoyl, 3-cyclopentenoyl, 1-cyclohexenoyl, 2-cyclohexenoyl,3-cyclohexenoyl, and the like.

“Cycloalkoxy” and “cycloalkoxycarbonyl” refer, respectively, tocycloalkyl-O— and cycloalkenyl-O, and to cycloalkyl-O—C(O)— andcycloalkenyl-O—C(O)—, where cycloalkyl and cycloalkenyl are definedabove. References to cycloalkoxy and cycloalkoxycarbonyl generallyinclude a specified number of carbon atoms, excluding the carbonylcarbon.

Examples of cycloalkoxy groups include, without limitation,cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexoxy, 1-cyclobutenoxy,2-cyclobutenoxy, 1-cyclopentenoxy, 2-cyclopentenoxy, 3-cyclopentenoxy,1-cyclohexenoxy, 2-cyclohexenoxy, 3-cyclohexenoxy, and the like.Examples of cycloalkoxycarbonyl groups include, without limitation,cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl,cyclohexoxycarbonyl, 1-cyclobutenoxycarbonyl, 2-cyclobutenoxycarbonyl,1-cyclopentenoxycarbonyl, 2-cyclopentenoxycarbonyl,3-cyclopentenoxycarbonyl, 1-cyclohexenoxycarbonyl,2-cyclohexenoxycarbonyl, 3-cyclohexenoxycarbonyl, and the like.

“Aryl” and “arylene” refer to monovalent and divalent aromatic groups,respectively, including 5- and 6-membered monocyclic aromatic groupsthat contain 0 to 4 heteroatoms independently selected from nitrogen,oxygen, and sulfur. Examples of monocyclic aryl groups include, withoutlimitation, phenyl, pyrrolyl, furanyl, thiopheneyl, thiazolyl,isothiazolyl, imidazolyl, triazolyl, tetrazolyl, pyrazolyl, oxazolyl,isooxazolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, and thelike. Aryl and arylene groups also include bicyclic groups, tricyclicgroups, etc., including fused 5- and 6-membered rings as describedabove. Examples of multicyclic aryl groups include, without limitation,naphthyl, biphenyl, anthracenyl, pyrenyl, carbazolyl, benzoxazolyl,benzodioxazolyl, benzothiazolyl, benzoimidazolyl, benzothiopheneyl,quinolinyl, isoquinolinyl, indolyl, benzofuranyl, purinyl, indolizinyl,and the like. The aryl and arylene groups may be attached to a parentgroup or to a substituent at any ring atom, unless such attachment wouldviolate valence requirements.

Likewise, aryl and arylene groups may include one or more non-hydrogensubstituents unless such substitution would violate valencerequirements. Useful substituents include, without limitation, alkyl,alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl,cycloalkenyl, alkoxy, cycloalkoxy, alkanoyl, cycloalkanoyl,cycloalkenoyl, alkoxycarbonyl, cycloalkoxycarbonyl, and halo, as definedabove, and hydroxy, mercapto, nitro, amino, and alkylamino.

“Heterocycle” and “heterocyclyl” refer to saturated, partiallyunsaturated, or unsaturated monocyclic or bicyclic rings having from 5to 7 or from 7 to 11 ring members, respectively. These groups have ringmembers made up of carbon atoms and from 1 to 4 heteroatoms that areindependently nitrogen, oxygen or sulfur, and may include any bicyclicgroup in which any of the above-defined monocyclic heterocycles arefused to a benzene ring. The nitrogen and sulfur heteroatoms mayoptionally be oxidized. The heterocyclic ring may be attached to aparent group or to a substituent at any heteroatom or carbon atom unlesssuch attachment would violate valence requirements. Likewise, any of thecarbon or nitrogen ring members may include a non-hydrogen substituentunless such substitution would violate valence requirements. Usefulsubstituents include, without limitation, alkyl, alkenyl, alkynyl,haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, cycloalkenyl, alkoxy,cycloalkoxy, alkanoyl, cycloalkanoyl, cycloalkenoyl, alkoxycarbonyl,cycloalkoxycarbonyl, and halo, as defined above, and hydroxy, mercapto,nitro, amino, and alkylamino.

Examples of heterocycles include, without limitation, acridinyl,azocinyl, benzimidazolyl, benzofuranyl, benzothiofuranyl,benzothiophenyl, benzoxazolyl, benzthiazolyl, benztriazolyl,benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl,carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl, chromenyl,cinnolinyl, decahydroquinolinyl, 2H, 6H-1,5,2-dithiazinyl,dihydrofuro[2,3-b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl,imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl,indolizinyl, indolyl, 3H-indolyl, isobenzofuranyl, isochromanyl,isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl,isoxazolyl, morpholinyl, naphthyridinyl, octahydroisoquinolinyl,oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl,1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxazolidinyl, pyrimidinyl,phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl,phenoxathiinyl, phenoxazinyl, phthalazinyl, piperazinyl, piperidinyl,pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl,pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole,pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl,pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl,quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl,tetrahydroquinolinyl, 6H-1,2,5-thiadiazinyl, 1,2,3-thiadiazolyl,1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl,thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl,thienoimidazolyl, thiophenyl, triazinyl, 1,2,3-triazolyl,1,2,4-triazolyl, 1,2,5-triazolyl, 1,3,4-triazolyl, and xanthenyl.

“Heteroaryl” and “heteroarylene” refer, respectively, to monovalent anddivalent heterocycles or heterocyclyl groups, as defined above, whichare aromatic. Heteroaryl and heteroarylene groups represent a subset ofaryl and arylene groups, respectively.

“Arylalkyl” and “heteroarylalkyl” refer, respectively, to aryl-alkyl andheteroaryl-alkyl, where aryl, heteroaryl, and alkyl are defined above.Examples include, without limitation, benzyl, fluorenylmethyl,imidazol-2-yl-methyl, and the like.

“Arylalkanoyl,” “heteroarylalkanoyl,” “arylalkenoyl,”“heteroarylalkenoyl,” “arylalkynoyl,” and “heteroarylalkynoyl” refer,respectively, to aryl-alkanoyl, heteroaryl-alkanoyl, aryl-alkenoyl,heteroaryl-alkenoyl, aryl-alkynoyl, and heteroaryl-alkynoyl, where aryl,heteroaryl, alkanoyl, alkenoyl, and alkynoyl are defined above. Examplesinclude, without limitation, benzoyl, benzylcarbonyl, fluorenoyl,fluorenylmethylcarbonyl, imidazol-2-oyl, imidazol-2-yl-methylcarbonyl,phenylethenecarbonyl, 1-phenylethenecarbonyl, 1-phenyl-propenecarbonyl,2-phenyl-propenecarbonyl, 3-phenyl-propenecarbonyl,imidazol-2-yl-ethenecarbonyl, 1-(imidazol-2-yl)-ethenecarbonyl,1-(imidazol-2-yl)-propenecarbonyl, 2-(imidazol-2-yl)-propenecarbonyl,3-(imidazol-2-yl)-propenecarbonyl, phenylethynecarbonyl,phenylpropynecarbonyl, (imidazol-2-yl)-ethynecarbonyl,(imidazol-2-yl)-propynecarbonyl, and the like.

“Arylalkoxy” and “heteroarylalkoxy” refer, respectively, to aryl-alkoxyand heteroaryl-alkoxy, where aryl, heteroaryl, and alkoxy are definedabove. Examples include, without limitation, benzyloxy,fluorenylmethyloxy, imidazol-2-yl-methyloxy, and the like.

“Aryloxy” and “heteroaryloxy” refer, respectively, to aryl-O— andheteroaryl-O—, where aryl and heteroaryl are defined above. Examplesinclude, without limitation, phenoxy, imidazol-2-yloxy, and the like.

“Aryloxycarbonyl,” “heteroaryloxycarbonyl,” “arylalkoxycarbonyl,” and“heteroarylalkoxycarbonyl” refer, respectively, to aryloxy-C(O)—,arylalkoxy-C(O)—, heteroarylalkoxy-C(O)—, where aryloxy, heteroaryloxy,arylalkoxy, and heteroarylalkoxy are defined above. Examples include,without limitation, phenoxycarbonyl, imidazol-2-yloxycarbonyl,benzyloxycarbonyl, fluorenylmethyloxycarbonyl,imidazol-2-yl-methyloxycarbonyl, and the like.

“alkylthio,” “alkenylthio,” “alkynylthio,” “alkoxythio,”“alkylthioalkyl,” and “arylthio,” refer, respectively, to —S-alkyl,—S-alkenyl, —S-alkynyl, —S-alkoxy, alkyl substituted with alkylthio, and—S-aryl, where alyl and aryl are defined above.

“Arylsulfonyl” and “arylsulfinyl” refer, respectively, to aryl-S(O₂)—and aryl-S(═O)—, where aryl is defined above.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims (e.g., bodies of theappended claims) are generally intended as “open” terms (e.g., the term“including” should be interpreted as “including but not limited to,” theterm “having” should be interpreted as “having at least,” the term“includes” should be interpreted as “includes but is not limited to,”etc.). It will be further understood by those within the art that if aspecific number of an introduced claim recitation is intended, such anintent will be explicitly recited in the claim, and in the absence ofsuch recitation no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should be interpreted to mean “at least one”or “one or more”); the same holds true for the use of definite articlesused to introduce claim recitations. In addition, even if a specificnumber of an introduced claim recitation is explicitly recited, thoseskilled in the art will recognize that such recitation should beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, means at leasttwo recitations, or two or more recitations). Furthermore, in thoseinstances where a convention analogous to “at least one of A, B, and C,etc.” is used, in general such a construction is intended in the senseone having skill in the art would understand the convention (e.g., “asystem having at least one of A, B, and C” would include but not belimited to systems that have A alone, B alone, C alone, A and Btogether, A and C together, B and C together, and/or A, B, and Ctogether, etc.). It will be further understood by those within the artthat virtually any disjunctive word and/or phrase presenting two or morealternative terms, whether in the description, claims, or drawings,should be understood to contemplate the possibilities of including oneof the terms, either of the terms, or both terms. For example, thephrase “A or B” will be understood to include the possibilities of “A”or “B” or “A and B.”

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, such as in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” “greater than,” “less than,” and the likeinclude the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember. Thus, for example, a group having 1-3 cells refers to groupshaving 1, 2, or 3 cells. Similarly, a group having 1-5 cells refers togroups having 1, 2, 3, 4, or 5 cells, and so forth.”

While various aspects and embodiments have been disclosed herein, otheraspects and embodiments will be apparent to those skilled in the art.The various aspects and embodiments disclosed herein are for purposes ofillustration and are not intended to be limiting, with the true scopeand spirit being indicated by the following claims. All referencesrecited herein are incorporated herein by specific reference in theirentirety.

The invention claimed is:
 1. A polymer and nanoparticle combinationcomprising: a conductive copolymer having one or more first conductivemonomers and one or more second conductive monomers, wherein the one ormore first conductive monomers and the one or more second conductivemonomers are copolymerized to form the conductive copolymer; aconductive nanoparticle covalently bound to a first end of a linker anda second end of the linker being covalently bound to the conductivecopolymer, the linker including at least one member selected from thegroup consisting of an alkylthio, an alkenylthio, and an alkynylthio;wherein the one or more first conductive monomers have a structureFormula 4 or an analog or derivative thereof:

where: X₂ is S; and R₃ and R₃′ are substituents and represent3,4-propylenedioxythiophene; and wherein the one or more secondconductive monomers have a structure of Formula 1:

where: A is thienylene vinylene, which is unsubstituted or substitutedwith one or more substituents, wherein the substituents areindependently selected from the group of hydrogen, hydroxyl, alkyl,alkenyl, alkynyl, alkanoyl, alkanoylamino, alkenoyl, alkynoyl, alkoxy,alkoxycarbonyl, alkoxycarbonylamino, alkylamino, alkylaminocarbonyl,dialkylaminocarbonyl, alkylsulfonyl, alkylsulfinyl, sulfonylaminoalkyl,alkylsulfonylaminocarbonyl, aminoalkyl, cyanoalkyl, halogen, haloalkyl,haloalkenyl, haloalkynyl, haloalkanoyl, haloalkenoyl, haloalkynoyl,haloalkoxy, haloalkoxycarbonyl, hydroxyalkyl, oxoalkyl, cycloalkyl,cycloalkenyl, cycloalkanoyl, cycloalkenoyl, cycloalkoxy,cycloalkoxycarbonyl, aryl, arylene, heterocycle, heterocyclyl,heteroaryl, heteroarylene, arylalkyl, heteroarylalkyl, arylalkanoyl,heteroarylalkanoyl, arylalkenoyl, heteroarylalkenoyl, arylalkynoyl,heteroarylalkynoyl, arylalkoxy, heteroarylalkoxy, aryloxy,heteroaryloxy, aryloxycarbonyl, heteroaryloxycarbonyl,arylalkoxycarbonyl, heteroarylalkoxycarbonyl, alkylthio, alkylthioalkyl,arylthio, arylsulfonyl and arylsulfinyl, or the substituents togethermay form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or7-membered aromatic or alicyclic ring having 0 or more divalentnitrogen, sulfur or oxygen atoms; and the substituents being substitutedor unsubstituted.
 2. The polymer and nanoparticle combination of claim1, wherein the conductive nanoparticle is linked to one or more of thefirst conductive monomers, and/or one or more of the second conductivemonomers.
 3. The polymer and nanoparticle combination of claim 1,wherein the polymer has a degree of polymerization in a range from 100to 1,000.
 4. The polymer and nanoparticle combination as in claim 1,wherein the conductive nanoparticle has one or more solvent compatiblegroups.
 5. The polymer and nanoparticle combination as in claim 4,wherein the solvent compatible groups are hydrophilic moieties.
 6. Thepolymer and nanoparticle combination of claim 1, wherein the linker isunsubstituted or substituted.
 7. The polymer and nanoparticlecombination of claim 1, wherein the conductive polymer includes one ormore cationic or anionic monomers.
 8. The polymer and nanoparticlecombination of claim 1, comprising one or more styrene sulfonatemonomers.
 9. A polymer and nanoparticle combination comprising: thepolymer having one or more first conductive monomers and one or moresecond conductive monomers that are copolymerized to form the copolymer;wherein the one or more first conductive monomers have a structure ofFormula 4 or an analog or derivative thereof:

where: X₂ is S; and R₃ and R₃′ are substituents and represent3,4-propylenedioxythiophene; and a conductive nanoparticle linked to theone or more conductive monomers through the R₃, or R₃′ substituent, theone or more conductive monomers covalently bound to a first end of alinker and a second end of the linker being covalently bound to theconductive nanoparticle, the linker including at least one memberselected from the group consisting of an alkylthio, an alkenylthio, andan alkynylthio; the one or more second conductive monomers have astructure of Formula 1:

where: A is thienylene vinylene, which is unsubstituted or substitutedwith one or more substituents, wherein the substituents areindependently selected from the group of hydroxyl, alkyl, alkenyl,alkynyl, alkanoyl, alkanoylamino, alkenoyl, alkynoyl, alkoxy,alkoxycarbonyl, alkoxycarbonylamino, alkylamino, alkylaminocarbonyl,dialkylaminocarbonyl, alkylsulfonyl, alkylsulfinyl, sulfonylaminoalkyl,alkylsulfonylaminocarbonyl, aminoalkyl, cyanoalkyl, halogen, haloalkyl,haloalkenyl, haloalkynyl, haloalkanoyl, haloalkenoyl, haloalkynoyl,haloalkoxy, haloalkoxycarbonyl, hydroxyalkyl, oxoalkyl, cycloalkyl,cycloalkenyl, cycloalkanoyl, cycloalkenoyl, cycloalkoxy,cycloalkoxycarbonyl, aryl, arylene, heterocycle, heterocyclyl,heteroaryl, heteroarylene, arylalkyl, heteroarylalkyl, arylalkanoyl,heteroarylalkanoyl, arylalkenoyl, heteroarylalkenoyl, arylalkynoyl,heteroarylalkynoyl, arylalkoxy, heteroarylalkoxy, aryloxy,heteroaryloxy, aryloxycarbonyl, heteroaryloxycarbonyl,arylalkoxycarbonyl, heteroarylalkoxycarbonyl, alkylthio, alkylthioalkyl,arylthio, arylsulfonyl and arylsulfinyl, or the substituents togethermay form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or7-membered aromatic or alicyclic ring having 0 or more divalentnitrogen, sulfur or oxygen atoms; and the substituents being substitutedor unsubstituted.
 10. The polymer and nanoparticle combination of claim9, wherein the polymer has a degree of polymerization in a range from100 to 1,000.
 11. An electronic device comprising the polymer andnanoparticle combination of claim
 9. 12. The polymer and nanoparticlecombination of claim 9, wherein the linker is unsubstituted orsubstituted.
 13. The polymer and nanoparticle combination of claim 9,wherein the polymer includes one or more cationic or anionic monomers.14. The polymer and nanoparticle combination of claim 9, wherein thepolymer includes one or more styrene sulfonate monomers.
 15. Acomposition comprising the polymer and nanoparticle combination of claim1 and a polymeric acid doped into the polymer.
 16. An electronic devicecomprising the polymer and nanoparticle combination of claim
 1. 17. Apolymer and nanoparticle combination comprising: a conductive copolymerhaving one or more first conductive monomers and one or more secondmonomers, wherein the one or more first conductive monomers and the oneor more second monomers are copolymerized to form the conductivecopolymer; a conductive nanoparticle covalently bound to a first end ofa linker and a second end of the linker being covalently bound to theconductive copolymer, so that the nanoparticle is indirectly linked tothe conductive polymer through the linker, the linker including at leastone member selected from the group consisting of an alkylthio, analkenylthio, and an alkynylthio; wherein the conductive nanoparticle isselected from the group consisting of gold, silver, copper, platinum,and palladium; wherein the one or more first conductive monomers have astructure of Formula 4 or an analog or derivative thereof:

where: X₂ is S; and R₃ and R₃′ are substituents and represent3,4-propylenedioxythiophene; and wherein the one or more second monomershave a structure of Formula 1:

where: A is thienylene vinylene, which is unsubstituted or substitutedwith one or more substituents, wherein the substituents areindependently selected from the group of hydrogen, hydroxyl, alkyl,alkenyl, alkynyl, alkanoyl, alkanoylamino, alkenoyl, alkynoyl, alkoxy,alkoxycarbonyl, alkoxycarbonylamino, alkylamino, alkylaminocarbonyl,dialkylaminocarbonyl, alkylsulfonyl, alkylsulfinyl, sulfonylaminoalkyl,alkylsulfonylaminocarbonyl, aminoalkyl, cyanoalkyl, halogen, haloalkyl,haloalkenyl, haloalkynyl, haloalkanoyl, haloalkenoyl, haloalkynoyl,haloalkoxy, haloalkoxycarbonyl, hydroxyalkyl, oxoalkyl, cycloalkyl,cycloalkenyl, cycloalkanoyl, cycloalkenoyl, cycloalkoxy,cycloalkoxycarbonyl, aryl, arylene, heterocycle, heterocyclyl,heteroaryl, heteroarylene, arylalkyl, heteroarylalkyl, arylalkanoyl,heteroarylalkanoyl, arylalkenoyl, heteroarylalkenoyl, arylalkynoyl,heteroarylalkynoyl, arylalkoxy, heteroarylalkoxy, aryloxy,heteroaryloxy, aryloxycarbonyl, heteroaryloxycarbonyl,arylalkoxycarbonyl, heteroarylalkoxycarbonyl, alkylthio, alkylthioalkyl,arylthio, arylsulfonyl and arylsulfinyl, or the substituents togethermay form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or7-membered aromatic or alicyclic ring having 0 or more divalentnitrogen, sulfur or oxygen atoms; and the substituents being substitutedor unsubstituted.
 18. A composition comprising the polymer andnanoparticle combination of claim 17, wherein the conductivenanoparticle is surrounded by hydrophilic moieties bonded thereto toincrease solubility of the polymer and nanoparticle combination inwater.